WO2018120702A1 - 半芳香族聚酰胺生产方法及半芳香族聚酰胺 - Google Patents

半芳香族聚酰胺生产方法及半芳香族聚酰胺 Download PDF

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WO2018120702A1
WO2018120702A1 PCT/CN2017/090830 CN2017090830W WO2018120702A1 WO 2018120702 A1 WO2018120702 A1 WO 2018120702A1 CN 2017090830 W CN2017090830 W CN 2017090830W WO 2018120702 A1 WO2018120702 A1 WO 2018120702A1
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acid
diamine
semi
dibasic acid
aromatic
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PCT/CN2017/090830
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English (en)
French (fr)
Inventor
陈志荣
尹红
张琴
吴笑笑
洪文刚
邓杭军
周贵阳
王昌泽
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浙江新和成特种材料有限公司
浙江大学
浙江新和成股份有限公司
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Priority to EP17854184.3A priority Critical patent/EP3366716B1/en
Priority to US15/779,414 priority patent/US10844171B2/en
Priority to KR1020187022855A priority patent/KR102077057B1/ko
Priority to JP2018521282A priority patent/JP6591670B2/ja
Publication of WO2018120702A1 publication Critical patent/WO2018120702A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/265—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids from at least two different diamines or at least two different dicarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • C08L77/08—Polyamides derived from polyamines and polycarboxylic acids from polyamines and polymerised unsaturated fatty acids

Definitions

  • the present invention relates to a process for producing semi-aromatic polyamides and semi-aromatic polyamides, and more particularly to a process for the continuous production of low-gel semi-aromatic polyamides.
  • the semi-aromatic polyamide is usually a polyamide having a benzene ring structure obtained by polycondensation of an aromatic dibasic acid, an aliphatic diacid and an aliphatic diamine. Due to the introduction of the aromatic ring structure in the main chain, the semi-aromatic polyamide has better heat resistance and mechanical properties, lower water absorption, and has a suitable cost performance, filling the general engineering plastic nylon and high temperature engineering.
  • the gap between plastic PEEK can be applied to the fields of electronics, electrical appliances, automobiles, clothing fibers and the like.
  • the preparation of semi-aromatic polyamides generally employs a prepolymerization-post-polycondensation reaction process.
  • the prepolymerization reaction usually uses water as a reaction solvent, and the dibasic acid and the diamine are first neutralized in a salt forming kettle to form a salt solution, and then heated to a certain temperature for dehydration and prepolymerization to obtain a prepolymer.
  • the prepolymer aqueous solution is flashed under reduced pressure to obtain a prepolymer solid or a melt; the prepolymer is further subjected to solid phase or melted and then polycondensed to obtain a semi-aromatic polyamide product having a certain molecular weight.
  • CN105377948A it is introduced that different ratios of terephthalic acid and isophthalic acid, aliphatic diamine, catalyst, molecular weight regulator are first batched into salt, and then continuously pre-precipitated.
  • the method requires a higher ratio of amine to acid in the salt formation process.
  • CN1678660A a process for continuously producing polyamide is described.
  • semi-aromatic polyamide it is an aromatic dibasic acid, an aliphatic dibasic acid, an aliphatic diamine, a catalyst, a molecular weight regulator.
  • the salt is firstly batched, and then the product is obtained by a continuous pipe prepolymerization reaction, a tank dehydration prepolymerization reaction, and a melt polycondensation reaction. After the prepolymerization reaction, the material is directly melted and then polycondensed, and the amount of the blocking agent is adjusted according to the outlet viscosity of the melt polycondensation reactor to achieve the purpose of stabilizing the viscosity of the polyamide.
  • a process for the continuous production of polyamides in which a molten acid-rich component mainly composed of an aliphatic dibasic acid is introduced from the top of a vertical multi-stage reactor, and the aliphatic diamine vapor is in a vertical section.
  • the lower portion of the reactor is introduced, and a method of preparing a polyamide by countercurrent continuous polycondensation in a reactor is carried out.
  • the method is equipped with a near-infrared analytical instrument near the outlet of the reactor, and the ratio of the terminal amine group to the terminal carboxyl group can be analyzed online, and the material ratio can be adjusted accordingly. Since the feed must be in a molten state, this method is mainly used for the preparation of nylon 6,6, and is not suitable for semi-aromatic polyamides having an aromatic dibasic acid content of more than 50%.
  • the present invention provides a polyamide production process and a low gel content polyamide, and more particularly to a process for producing a continuous low gel content semi-aromatic polyamide.
  • a first aspect of the invention provides a semi-aromatic polyamide production method comprising:
  • Step 1 the initial charge of the diamine and the dibasic acid according to the molar ratio of the amine acid is less than 1.0, forming a slurry with water and the catalyst, and the slurry is heated and dissolved to form a salt solution.
  • Step 2 after detecting the composition of the salt solution, dehydrating the salt solution, detecting the content of the diamine in the steam condensed water from the dehydration device, and adjusting the amine acid molar ratio by using the diamine and the molecular weight regulator monobasic acid To a prepolymerization reaction of more than 1.0,
  • step 3 the prepolymerization reaction liquid is flashed under reduced pressure to carry out a post polycondensation reaction.
  • the molar ratio of the initial acid to be fed in the step 1 is from 0.90 to 0.99, preferably from 0.92 to 0.98.
  • the dibasic acid comprises an aromatic dibasic acid and an aliphatic dibasic acid
  • the molar ratio of the aromatic dibasic acid to the aliphatic dibasic acid is from 100:0 to 40:60, preferably 100. : 0 to 50:50.
  • the aliphatic dibasic acid is selected from the group consisting of succinic acid, glutaric acid, adipic acid, and bis One or more of an acid, azelaic acid, sebacic acid, and dodecanedioic acid, the aromatic dibasic acid being selected from one of isophthalic acid, terephthalic acid, naphthalene dicarboxylic acid or Several.
  • the diamine is selected from the group consisting of diamine, heptanediamine, octanediamine, decanediamine, decanediamine, 2-methylpentanediamine, undecyldiamine, and twelteen methylene
  • a diamine, a dimethylenediamine preferably the diamine is selected from one or more of its own diamine, octane diamine, and decanediamine.
  • the molecular weight regulator monocarboxylic acid is selected from the group consisting of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, palmitic acid, palmitic acid, stearic acid, benzoic acid or One or more of phenylacetic acid.
  • the number of moles of the molecular weight regulator monobasic acid is from 0.1 to 5%, preferably from 0.5 to 3%, based on the total moles of the dibasic acid in the initial charge.
  • the mass of the catalyst is from 0.01 to 2.5% based on the total mass of the dibasic acid in the initial charge.
  • the step 1 further comprises the step of detecting the composition of the dibasic acid in the salt solution by adding an aromatic dibasic acid and/or an aliphatic dibasic acid to maintain the stability of the dibasic acid composition.
  • the detection in the step 1 employs online Raman spectroscopy.
  • the detection in the step 2 employs an online Raman spectrum.
  • the molar ratio of the amine acid in the step 2 is from 1.00 to 1.05, preferably from 1.01 to 1.04.
  • the dehydration temperature is 170-260 ° C
  • the pressure is 0.7-2.0 MPa
  • the dehydration time is 10-40 min.
  • the temperature of the prepolymerization reaction is 250-350 ° C
  • the pressure is 10-30 MPa
  • the reaction time is 1-15 min.
  • the reaction temperature of the post-polycondensation reaction is 300-350 ° C, and the reaction time is 0.5-5min.
  • the water vapor generated in the dehydration step in the step 2 can be used as a heat source for the temperature rise and dissolution of the slurry, and the excess water vapor can be combined with the condensed water generated in the heating process after the condensation to be used as the supplementary water for forming the slurry. Process of materials.
  • a second aspect of the invention provides a semi-aromatic polyamide which is prepared according to the above method and has a gel content of 1.0% or less, preferably 0.8% or less.
  • a third aspect of the invention provides a semi-aromatic polyamide obtained by a polycondensation reaction of a dibasic acid and an aliphatic diamine, the aromatic acid comprising an aromatic dibasic acid, an aliphatic dibasic acid,
  • the molar ratio of the aromatic dibasic acid to the aliphatic dibasic acid is from 100:0 to 40:60, preferably from 100:0 to 50:50; and the gel content is 1.0% or less, preferably 0.8% or less.
  • the aliphatic dibasic acid is selected from one of succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid.
  • One or more of the aromatic dibasic acids are selected from one or more of isophthalic acid, terephthalic acid, and naphthalene dicarboxylic acid.
  • the diamine is selected from the group consisting of self-diamine, heptanediamine, octanediamine, decanediamine, decanediamine, 2-methylpentanediamine, undecyldiamine.
  • the semi-aromatic polyamide has an intrinsic viscosity of 0.7 to 1.0 dl/g.
  • the inventors' research has shown that in the production method of the semi-aromatic polyamide, the molar ratio of the amine acid is less than 1.0 in the formation of the slurry, the dissolution into the salt, and the dehydration process, and the dehydration, prepolymerization, and postpolycondensation reaction are appropriately controlled. Time can reduce the degree of gelation.
  • the obtained semi-aromatic polyamide has a low gel content, good fluidity, and high mechanical strength, and can be adapted to different post-processing requirements.
  • the steam generated by the dehydration process is used for dissolving the heating of the salt forming process, thereby reducing the energy consumption of the process; the excess water vapor can be combined with the condensed water generated in the heating process after condensation.
  • the addition of water is used to form a slurry to reduce the discharge of process wastewater.
  • the on-line detection of the composition in the salt solution before dehydration (including the molar ratio of the amine acid) and the content of the diamine in the steam condensed water from the dehydration unit can be used in the production process according to the actual situation. Adjust the proportion of each raw material. For example, according to Raman spectroscopy results, the molten aliphatic dibasic acid and the aromatic dibasic acid slurry and the molten diamine can be used to continuously fine-tune the composition of the reaction material, thereby achieving complete continuation of the production process; The addition of the regulator after dehydration can avoid the loss caused by dehydration, so as to achieve precise control of the ratio.
  • multi-channel on-line Raman spectroscopy is used to continuously and quantitatively determine the content of each component when the ratio of amine to acid is less than 1.0 according to the characteristic Raman absorption peak of different raw materials, thereby being continuous in the production process. Adjust the proportion of raw materials and stabilize the production process.
  • the production process can be completely continuous and the energy consumption is low; the obtained product has low gel content, excellent performance and wide application fields.
  • Figure 1 shows the normalized Raman spectrum (600 to 1200 cm-1) of various nylon salts.
  • Figure 2 shows the normalized Raman spectrum (1200 - 1800 cm-1) of various nylon salts.
  • Figure 3 shows a process flow diagram of an embodiment of the invention.
  • a first aspect of the invention provides a method for producing a semi-aromatic polyamide, comprising:
  • Step 1 the initial charge of the diamine and the dibasic acid according to the molar ratio of the amine acid is less than 1.0, forming a slurry with water and the catalyst, and the slurry is heated and dissolved to form a salt solution.
  • Step 2 after detecting the composition of the salt solution, dehydrating the salt solution, detecting the content of the diamine in the steam condensed water from the dehydration device, and adjusting the amine acid mole by using the molten diamine and the molecular weight regulator monobasic acid Prepolymerization is carried out at a ratio greater than 1.0.
  • step 3 the prepolymerization reaction liquid is flashed under reduced pressure to carry out a post polycondensation reaction.
  • the dibasic acid includes an aromatic dibasic acid and an aliphatic dibasic acid, and the molar ratio of the two is from 100:0 to 40:60, preferably from 100:0 to 50:50.
  • the aliphatic dibasic acid is selected from one or more of succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid, preferably adipic acid. Or one or more of suberic acid, sebacic acid, and dodecanedioic acid; and the aromatic dibasic acid is selected from one or more of isophthalic acid, terephthalic acid, and naphthalene dicarboxylic acid; One or more of isophthalic acid and terephthalic acid are preferred.
  • the diamine is selected from the group consisting of diamine, heptanediamine, octanediamine, decanediamine, decanediamine, 2-methylpentanediamine, undecyldiamine, and t-methylenediamine.
  • One or more of phenylenediethylenediamine, preferably the diamine is selected from one or more of its own diamine, octane diamine, and decanediamine.
  • the molecular weight regulator monobasic acid is selected from the group consisting of acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, palmitic acid, palmitic acid, stearic acid, benzoic acid or phenylacetic acid.
  • the molar amount of the molecular weight modifier to be added is 0.1 to 5%, preferably 0.5 to 3%, based on the total molar amount of the raw material dicarboxylic acid.
  • the initial feed amine acid molar ratio is less than 1.0, preferably the initial acid feed molar ratio is More preferably, the initial charge amine acid molar ratio is from 0.90 to 0.99.
  • the semi-aromatic polyamide production method may employ a phosphorus-based compound as a catalyst.
  • Phosphorus-based compounds include, for example, phosphoric acid, phosphorous acid, hypophosphorous acid and salts or ester derivatives thereof such as phosphoric acid, phosphorous acid or hypophosphorous acid, or sodium, potassium, magnesium, vanadium, calcium of phosphoric acid, phosphorous acid or metal hypophosphite , zinc, cobalt, manganese, tin, tungsten, tantalum, titanium or strontium salts; ammonium phosphate, ammonium phosphite and ammonium diphosphate; ethyl phosphate, isopropyl ester, butyl phosphate of phosphoric acid, phosphorous acid or hypophosphorous acid , hexyl ester, isodecyl ester, octadecyl ester, decyl ester, octadecyl ester or
  • the catalyst is preferably one or more selected from the group consisting of sodium phosphate, potassium phosphate, sodium phosphite, potassium phosphite, sodium hypophosphite, and potassium hypophosphite.
  • the mass of the catalyst is from 0.01 to 2.5%, preferably from 0.05 to 1%, based on the total mass of the dibasic acid in the initial charge.
  • the step 1 further comprises: detecting the composition of the dibasic acid in the salt solution, and maintaining the dibasic acid by adding an aromatic dibasic acid and/or an aliphatic dibasic acid.
  • detecting the composition of the dibasic acid in the salt solution and maintaining the dibasic acid by adding an aromatic dibasic acid and/or an aliphatic dibasic acid.
  • Form a stable step For example, online Raman spectroscopy is used to determine the composition of the dibasic acid in the salt solution.
  • the composition of the dibasic acid in the salt solution is adjusted by using a molten aliphatic dibasic acid and/or an aromatic dibasic acid slurry. To keep it stable.
  • the molar ratio of the amine acid in the salt solution before dehydration and the content of the diamine in the steam condensed water from the dehydration device are detected by on-line Raman spectroscopy, and the binary is used according to the detection result.
  • the amine and molecular weight regulator monobasic acid adjusts the amine acid molar ratio to greater than 1.0.
  • the use of the diamine and the molecular weight regulator monobasic acid to adjust the amine acid molar ratio to more than 1.0 means the sum of the adjusted aliphatic diamine and the aliphatic dibasic acid, the aromatic dibasic acid and the molecular weight regulator monobasic acid
  • the amine acid molar ratio is controlled to be greater than 1.0, preferably from 1.00 to 1.05, more preferably from 1.01 to 1.04.
  • a method for producing a semi-aromatic polyamide is provided, and further, a method for continuously producing a semi-aromatic polyamide is provided.
  • online Raman spectroscopy is used to determine the composition of the dibasic acid in the salt solution.
  • the composition of the dibasic acid in the salt solution is adjusted by using a molten aliphatic dibasic acid and/or an aromatic dibasic acid slurry. To keep it stable.
  • the content of the diamine in the steam condensed water coming out is adjusted by the diamine and the molecular weight regulator monobasic acid to a molar ratio of more than 1.0 according to the detection result.
  • the water vapor desorbed in the dehydration stage can be used as a heat source for the temperature-increasing dissolution process of the slurry, and the excess water vapor can be combined with the condensed water generated in the heating process after condensation as a process of adding water for forming the slurry.
  • the system may have a water content of from 10 to 50%, preferably from 15 to 30%, and a temperature of from 50 to 95 ° C, preferably from 60 to 90 ° C, in the step of forming a slurry.
  • the temperature at which the salt is dissolved may be from 120 to 170 ° C, preferably from 130 to 160 ° C.
  • the dehydration temperature may be 170-260 ° C, preferably 190-240 ° C; the pressure may be 0.7-2.0 MPa, preferably 1.0-1.8 MPa; the dehydration time may be 10-40 min, preferably 15-30 min.
  • the water content after dehydration is 5-20%, preferably 7-15%.
  • the prepolymerization reaction temperature may be 250-350 ° C, preferably 280-340 ° C; the pressure may be 10-30 MPa, preferably 15-25 MPa; the reaction time may be 1-15 min, preferably It is 2-10min.
  • the vacuum flash pressure after the prepolymerization reaction may be from 0.15 to 0.9 MPa, preferably from 0.2 to 0.6 MPa, and the temperature may be the same as the temperature of the prepolymerization reaction.
  • the prepolymer is melted into the twin-screw extruder for post-polycondensation reaction, and the reaction temperature may be 300-350 ° C, preferably 310-340 ° C; the reaction time may be 0.5-5 min, preferably 1- 3min.
  • a diamine having an initial charge amine acid molar ratio of less than 1.0 is continuously slurried together with an aliphatic dibasic acid, an aromatic dibasic acid, and water and a catalyst to form a slurry.
  • the preheater is heated and heated to form a salt by steam generated by a dehydration process.
  • the salt solution is introduced into the dehydrator for temperature rise and dehydration, and the material before dehydration is detected by on-line Raman spectroscopy, and combined with the online Raman spectroscopy analysis of the diamine in the steam condensed water during dehydration, using the molten diamine and the molecular weight regulator
  • the monobasic acid adjusts the molar ratio of the amine to 1.005-1.05; then enters the prepolymerization reactor for temperature prepolymerization.
  • the prepolymerization reaction liquid is flashed under reduced pressure, and then enters a twin-screw extruder for post-polycondensation reaction, and then granulated and dried by underwater to obtain a low-gel semi-aromatic polyamide product.
  • a second aspect of the present invention provides a semi-aromatic polyamide having a gel content of 1.0% or less, preferably 0.8% or less, more preferably 0.5% or less, and most preferably 0.3% or less.
  • the semi-aromatic polyamide which is produced by the production method provided by the first aspect of the invention.
  • a third aspect of the present invention provides a semi-aromatic polyamide obtained by a polycondensation reaction of a dibasic acid and an aliphatic diamine, which includes an aromatic dibasic acid and an aliphatic dibasic acid.
  • the molar ratio of the aromatic dibasic acid to the aliphatic dibasic acid is from 100:0 to 40:60, preferably from 100:0 to 50:50; and the gel content is 1.0% or less, preferably 0.8% or less. It is more preferably 0.5% or less, and most preferably 0.3% or less.
  • the intrinsic viscosity [ ⁇ ] of the semi-aromatic polyamide is preferably 0.7 to 1.0 dL/g.
  • the fluidity at the time of molding of the resin composition containing the above semi-aromatic polyamide can be improved, and the mechanical properties of the obtained molded article are also improved.
  • the intrinsic viscosity [ ⁇ ] of the semi-aromatic polyamide is too low, the melt tension of the resin composition containing the same tends to be lower than a desired range.
  • the sample was dissolved in a mixed solvent of phenol-tetrachloroethane (mass ratio: 3:2) to obtain a solution having a concentration of 0.1, 0.5, and 1.0 g/dL, and an Ubbelohde viscometer was used in a constant temperature water bath at 30 ° C. The inherent viscosity number ⁇ ln of the sample solution is measured.
  • t 0 is the flow time (seconds) of the solvent
  • t is the flow time (seconds) of the solution
  • C is the concentration (g/dL) of the sample solution.
  • the invention uses the following Raman spectral information to determine the content of each component:
  • the content of isophthalic acid (IA) and its salt (6I) is determined by characteristic peaks at 1005 cm -1 and 762 cm -1 ;
  • TA terephthalic acid
  • 6T 6T
  • the content of diamine (HDA) was determined by a characteristic peak at 1485 cm -1 .
  • the composition of the dibasic acid in the salt solution is detected, and the amount of the aliphatic dibasic acid is adjusted by the metering pump 23 by using molten adipic acid to dissolve the aromatic dibasic acid and the aliphatic two in the salt kettle 19 The proportion of the acid remained stable.
  • the above salt solution is detected by the online Raman spectroscopy 20, it is pressurized by the pump 24 to 1.2 MPa, and then sent to the preheater (heat exchanger) 27 of the dehydrator before being mixed with the material conveyed by the circulation pump 28, and then heated.
  • the dehydrator 29 was dehydrated, the dehydration temperature was controlled at 190 ° C, the water content was controlled at 15%, and the dehydration residence time was 30 min.
  • the steam from the dehydrator serves as a heat source for the multistage stirred dissolution vessel 14, and after cooling by the heat exchanger 15, the amine content therein is detected by the online Raman spectrum 16.
  • the amount of replenished hexamethylenediamine required for pump 32 is determined by controller 21; the dehydrated material is passed through pump 17, pump 30, and hexamethylenediamine and 0.06 Kg/h, respectively. (1 mol/h) molecular weight regulator acetic acid adjusted amino acid molar ratio to 1.01.
  • the pump 32 is used to pressurize to 10 MPa, the material is sent to the preheater (heat exchanger) 33 for preheating to 280 ° C, and the prepolymerization reactor 34 is kept at 280 ° C for 5 min; the prepolymerized reaction solution is reduced.
  • the pressure valve 35 is depressurized to 0.2 MPa and then enters the flasher 36.
  • the molten liquid material is depressurized to a normal pressure through a pressure reducing valve 37, and then enters a twin-screw extruder 38 to carry out a post-polycondensation reaction at a reaction temperature of 300-310 ° C and a reaction residence time of 5 min.
  • the post-polycondensation reaction material was granulated in an underwater granulator 39, and dried by a dryer 40 to obtain a low-gel semi-aromatic polyamide product having an intrinsic viscosity IV of 0.92 dL/at about 11.8 kg/h. g, the amount of gel was 0.21%.
  • the slurry is sent to the multistage stirred dissolution vessel 14 via the pump 10, heated to a temperature of 160 ° C by steam generated in the dehydration process to dissolve into a salt, and the composition of the dibasic acid in the salt solution is detected according to the online Raman spectrum 18.
  • the amount of the aliphatic dibasic acid is adjusted by the metering pump 23 using the molten sebacic acid, and the ratio of the aromatic dibasic acid to the aliphatic dibasic acid in the salt forming kettle 19 is maintained stable.
  • the above salt solution is detected by the online Raman spectroscopy 20, it is pressurized by the pump 24 to 1.8 MPa, and then sent to the preheater (heat exchanger) 27 of the dehydrator before being mixed with the material conveyed by the circulation pump 28, and then heated.
  • the dehydrator 29 was dehydrated, the dehydration temperature was controlled at 240 ° C, the water content was controlled at 7%, and the dehydration residence time was 15 min.
  • the steam from the dehydrator serves as a heat source for the multistage stirred dissolution vessel 14, and is cooled by the heat exchanger 15 to detect the amine content therein by the online Raman spectrum 16.
  • the controller 21 determines the amount of supplemental molten guanidine diamine required prior to pump 32.
  • the dehydrated materials were adjusted by the pump 17, the pump 30 with molten guanidine diamine and 0.34 Kg / h (2 mol / h) molecular weight modifier citric acid to adjust the amino acid molar ratio to 1.02, and then pumped to 25 MPa with the pump 32, the material
  • the temperature was preheated to 340 ° C in the preheater (heat exchanger) 33, and the reaction was kept at 340 ° C for 2 min in the prepolymerization reactor 34.
  • the pre-polymerization reaction solution is depressurized to 0.6 MPa through the pressure reducing valve 35, and then enters the flasher 36. After flashing, the molten liquid material is depressurized to a normal pressure through a pressure reducing valve 37, and then enters the twin-screw extruder 38 for post-polycondensation reaction.
  • the reaction temperature is 320-330 ° C
  • the reaction residence time is 3 min.
  • the post-polycondensation reaction material was granulated in an underwater granulator 39, and dried by a dryer 40 to obtain a low-gel semi-aromatic polyamide product having an IV of 0.78 dL/g at about 16.7 kg/h. The amount of gel was 0.23%.
  • the composition of the dibasic acid in the salt solution is detected according to the online Raman spectrum 18, and the amount of the aliphatic dibasic acid is adjusted by the metering pump 23 by using the molten dodecanedioic acid to dissolve the aromatic dibasic acid and the fat in the salt kettle 19 The proportion of the dibasic acid remains stable.
  • the above salt solution is detected by the online Raman spectroscopy 20, it is pressurized by the pump 24 to 1.5 MPa and then sent to the preheater (heat exchanger) 27 of the dehydrator before being mixed with the material conveyed by the circulation pump 28, and then heated.
  • the dehydrator 29 was dehydrated, the dehydration temperature was controlled at 220 ° C, and the dehydration residence time was 20 min.
  • the steam from the dehydrator serves as a heat source for the multistage stirred dissolution vessel 14, and after cooling by the heat exchanger 15, the amine content therein is detected by the online Raman spectrum 16.
  • the amount of replenished hexamethylenediamine required for pump 32 is determined by controller 21; the dehydrated material is passed through pump 17, pump 30, and hexamethylenediamine and 0.27 Kg/h, respectively. (2 mol/h) molecular weight regulator phenylacetic acid adjusted amino acid molar ratio to 1.04.
  • the pump 32 is used to pressurize to 20 MPa, the material is sent to the preheater (heat exchanger) 33 for preheating to 320 ° C, and the prepolymerization reactor 34 is kept at 320 ° C for 3 min; the prepolymerized reaction solution is reduced.
  • the pressure valve 35 is decompressed to 0.4 MPa, it enters the flasher 36.
  • the molten liquid material is depressurized to a normal pressure through a pressure reducing valve 37, and then enters the twin-screw extruder 38 for post-polycondensation reaction, and the reaction temperature is 310-320. °C, reaction residence time 4min.
  • the post-polycondensation reaction material was granulated in an underwater granulator 39, and dried by a dryer 40 to obtain a low-gel semi-aromatic polyamide product having an IV of 0.72 dL/g at about 13.2 kg/h.
  • the amount of gel was 0.20%.
  • the composition of the dibasic acid in the salt solution is determined according to the online Raman spectrum 18.
  • the amount of the aliphatic dibasic acid is adjusted by the metering pump 23 using molten suberic acid to stabilize the ratio of the aromatic dibasic acid and the aliphatic dibasic acid dissolved in the salt kettle 19.
  • After the above salt solution is detected by the online Raman spectroscopy 20, it is pressurized by the pump 24 to 0.7 MPa, and then sent to the preheater (heat exchanger) 27 of the dehydrator before being mixed with the material conveyed by the circulation pump 28, and then heated.
  • the dehydrator 29 was dehydrated, the dehydration temperature was controlled at 170 ° C, the water content was controlled at 20%, and the dehydration residence time was 30 min.
  • the steam from the dehydrator serves as a heat source for the multistage stirred dissolution vessel 14, and is cooled by the heat exchanger 15 to detect the amine content therein by the online Raman spectrum 16.
  • the amount of supplemental molten dodecamethylene diamine required for pump 32 prior to pump 32 is determined by controller 21.
  • the dehydrated materials are adjusted by the pump 17, the pump 30 with molten dodecamethylene diamine and 0.05 Kg / h (0.25 mol / h) molecular weight regulator lauric acid to adjust the amine acid molar ratio to 1.005, and then pressurized by the pump 32
  • the material is sent to a preheater (heat exchanger) 33 for preheating to 330 ° C, and the reaction is held in a prepolymerization reactor 34 at 330 ° C for 3 min; the prepolymerized reaction solution is depressurized through a pressure reducing valve 35. After 0.15 MPa, it enters the flasher 36.
  • the molten liquid material is depressurized to a normal pressure through a pressure reducing valve 37, and then enters the twin-screw extruder 38 for post-polycondensation reaction, the reaction temperature is 340-350 ° C, and the reaction residence time is 0.5. Min.
  • the post-polycondensation reaction material was granulated in an underwater granulator 39, and dried by a dryer 40 to obtain a low-gel semi-aromatic polyamide product having an IV of 0.98 dL/g at about 16.7 kg/h. The amount of gel was 0.27%.
  • the slurry is sent to the multistage stirred dissolution vessel 14 via the pump 10 and heated to a temperature of 170 ° C by steam generated in the dehydration process to dissolve into a salt, and the composition of the dibasic acid in the salt solution is detected according to the online Raman spectrum 18.
  • the amount of the aliphatic dibasic acid is adjusted by the metering pump 23 using molten succinic acid, and the ratio of the aromatic dibasic acid to the aliphatic dibasic acid in the salt forming kettle 19 is maintained stable.
  • the above salt solution is detected by the online Raman spectroscopy 20, it is pressurized by the pump 24 to 2.0 MPa, and then sent to the preheater (heat exchanger) 27 of the dehydrator before being mixed with the material conveyed by the circulation pump 28, and then heated.
  • the dehydrator 29 was dehydrated, the dehydration temperature was controlled at 260 ° C, the water content was controlled at 5%, and the dehydration residence time was 10 min.
  • the steam from the dehydrator serves as a heat source for the multistage stirred dissolution vessel 14, and is cooled by the heat exchanger 15 to detect the amine content therein by the online Raman spectrum 16.
  • the controller 21 determines the amount of supplemental molten 2-methylpentanediamine required prior to pump 32.
  • the dehydrated materials were adjusted to a molar ratio of acid to acid of 1.05 by pump 17, pump 30 with molten 2-methylpentanediamine and 0.22 Kg/h (2.5 mol/h) molecular weight regulator butyric acid.
  • the pump 32 was used to pressurize to 27 MPa, and the material was sent to a preheater (heat exchanger) 33 for preheating to 320 ° C, and the reaction was kept at 320 ° C for 3 min in the prepolymerization reactor 34.
  • the prepolymerization reaction solution is depressurized to 0.9 MPa through the pressure reducing valve 35, and then enters the flasher 36. After the flashing, the molten liquid material is depressurized to a normal pressure through a pressure reducing valve 37, and then enters the twin-screw extruder 38 for post-polycondensation. Reaction, reaction temperature 320-330 ° C, reaction residence time 3 min.
  • the post-polycondensation reaction material was granulated in an underwater granulator 39, and dried by a dryer 40 to obtain a low-gel semi-aromatic polyamide product having an IV of 0.72 dL/g at about 12.5 kg/h. The amount of gel was 0.25%.
  • the slurry is sent to the multistage stirred dissolution vessel 14 via the pump 10, heated by steam generated in the dehydration process to 165 ° C to dissolve into a salt, and the composition of the dibasic acid in the salt solution is detected according to the online Raman spectrum 18.
  • the amount of isophthalic acid was adjusted by the metering pump 26 using a 50% isophthalic acid slurry to stabilize the ratio of terephthalic acid to isophthalic acid dissolved in the salt kettle 19.
  • the above salt solution is detected by the online Raman spectroscopy 20, it is pressurized by the pump 24 to 1.8 MPa, and then sent to the preheater (heat exchanger) 27 of the dehydrator before being mixed with the material conveyed by the circulation pump 28, and then heated.
  • the dehydrator 29 was dehydrated, the dehydration temperature was controlled at 235 ° C, the water content was controlled at 8%, and the dehydration residence time was 15 min.
  • the steam from the dehydrator serves as a heat source for the multistage stirred dissolution vessel 14, and is cooled by the heat exchanger 15 to detect the amine content therein by the online Raman spectrum 16.
  • the controller 21 determines the amount of supplemental molten hexamethylene diamine required prior to pump 32.
  • the dehydrated materials are adjusted by the pump 17, the pump 30 with molten hexamethylene diamine and 0.11 Kg / h (1.5 mol / h) molecular weight regulator propionic acid to adjust the amino acid molar ratio to 1.025, and then pumped to 25 MPa with the pump 32,
  • the material was transferred to a preheater (heat exchanger) 33 and preheated to 330 ° C, and held in a prepolymerization reactor 34 at 330 ° C for 2.5 min.
  • the pre-polymerization reaction solution is depressurized to 0.3 MPa through the pressure reducing valve 35, and then enters the flasher 36.
  • the molten liquid material is depressurized to a normal pressure through a pressure reducing valve 37, and then enters the twin-screw extruder 38 for post-polycondensation reaction.
  • the reaction temperature is 330-340 ° C
  • the reaction residence time is 2 min.
  • the post-polycondensation reaction material was granulated in an underwater granulator 39, and dried by a dryer 40 to obtain a low-gel semi-aromatic polyamide product having an IV of 0.77 dL/g at about 12.4 kg/h. The amount of gel was 0.20%.
  • the flow rate is pressurized by the pump 43 to 1.2 MPa, and then sent to the preheater (heat exchanger) 44 of the dehydrator before being mixed with the material conveyed by the circulation pump 45, and then heated, dehydrated in the dehydrator 46, and the dehydration temperature is controlled at 190 ° C.
  • the water content is controlled at 15%, the dehydration residence time is 30 min; the dehydrated material is pressurized to 10 MPa by the pump 48, and the material is sent to the preheater (heat exchanger) 49 for preheating to 280 ° C, in the prepolymerization.
  • the reaction is kept at 280 ° C for 5 min; the prepolymerized reaction solution is depressurized to 0.2 MPa through the pressure reducing valve 51, and then enters the flasher 52.
  • the flashed molten liquid material is depressurized to normal pressure and then enters the twin-screw extruder 54.
  • the post-polycondensation reaction was carried out at a reaction temperature of 300-310 ° C and a reaction residence time of 5 min; the post-polycondensation reaction was granulated in an underwater granulator 55, and dried by a dryer 56 to obtain about 11.6 kg/h.
  • a semi-aromatic polyamide product having an IV of 0.98 dL/g and a gel content of 1.03%.
  • the dehydration residence time is 15 min; the dehydrated material is pressurized to 25 MPa by the pump 48, and the material is sent to the preheater (heat exchanger) 49 for preheating to 340 ° C, in the prepolymerization reactor 50 at 340 The temperature is kept at ° C for 2 min; the prepolymerization reaction solution is depressurized to 0.6 MPa through the pressure reducing valve 51, and then enters the flasher 52. The flashed molten liquid material is decompressed to normal pressure and then enters the twin-screw extruder 54 for post-polycondensation reaction.
  • the reaction temperature is 320-330 ° C, the reaction residence time is 3 min; the material after the polycondensation reaction is granulated under water. 55 granulated, and then dried by a dryer 56, from about 16.6Kg / h to give a semi-aromatic polyamides, with an IV of 0.81dL / g, the gel in an amount of 1.12%.
  • the time is 20 min; the dehydrated material is pressurized to 20 MPa by the pump 48, the material is sent to the preheater (heat exchanger) 49, and the temperature is preheated to 320 ° C, and the reaction is kept at 320 ° C for 3 min in the prepolymerization reactor 50.
  • the prepolymerization reaction solution is depressurized to 0.4 MPa through the pressure reducing valve 51, and then enters the flasher 52.
  • the flashed molten liquid material is depressurized to normal pressure and then enters the twin-screw extruder 54 to carry out a post-polycondensation reaction, and the reaction temperature is 310- 320 ° C, reaction residence time 4 min; the material after the polycondensation reaction in the underwater granulator 55 Granulated, and then dried by a dryer 56, from about 13.0Kg / h to give a semi-aromatic polyamides, with an IV of 0.78dL / g, the gel in an amount of 2.51%.
  • Potassium phosphate aqueous solution 0.4 Kg (2 mol) of molecular weight regulator lauric acid and 61.1 Kg of water were put into a salt kettle 41 or 42 (switched every 8 hours) and heated to 130 ° C to dissolve into a salt; the above salt solution was 26.4 Kg /
  • the h flow rate is pressurized by the pump 43 to 0.7 MPa and then sent to the preheater (heat exchanger) 44 of the dehydrator before being mixed with the material conveyed by the circulation pump 45, and then heated, dehydrated in the dehydrator 46, and the dehydration temperature is controlled at 170.
  • the water content is controlled at 20%, the dehydration residence time is 30min;
  • the material is pressurized to 30 MPa by the pump 48, and the material is sent to the preheater (heat exchanger) 49 for preheating to 330 ° C, and the reaction is kept at 330 ° C for 3 min in the prepolymerization reactor 50; the prepolymerized reaction solution is passed through The pressure reducing valve 51 is depressurized to 0.15 MPa and then enters the flasher 52.
  • the flashed molten liquid material is depressurized to normal pressure and then enters the twin-screw extruder 54 for post-polycondensation reaction, the reaction temperature is 340-350 ° C, and the reaction residence time is 0.5 min; the post-polycondensation material was granulated in an underwater granulator 55, and dried by a dryer 56 to obtain a semi-aromatic polyamide product having an IV of 1.02 dL/g at about 16.6 kg/h. The amount of gel was 0.97%.
  • the water content is controlled at 5%, the dehydration residence time is 10 min; the dehydrated material is pressurized to 27 MPa with pump 48, and the material is sent to the preheater (heat exchanger) 49 for preheating to 320 ° C.
  • the reaction is kept in the prepolymerization reactor 50 at 320 ° C for 3 min; the prepolymerization reaction solution is depressurized to 0.9 MPa through the pressure reducing valve 51, and then enters the flasher 52.
  • the flashed molten liquid material is decompressed to normal pressure and then enters the twin screw.
  • the post-polycondensation reaction is carried out in the extruder 54, the reaction temperature is 320-330 ° C, and the reaction residence time is 3 min;
  • the polyreacted material was granulated in an underwater granulator 55 and dried by a dryer 56 to obtain a semi-aromatic polyamide product having an IV of 0.79 dL/g and a gel amount of 2.35 at about 12.4 kg/h. %.
  • the pump 43 After being pressurized by the pump 43 to 1.8 MPa, it is sent to the preheater (heat exchanger) 44 of the dehydrator and mixed with the material conveyed by the circulation pump 45, and then heated, dehydrated in the dehydrator 46, and the dehydration temperature is controlled at 235 ° C.
  • the water content is controlled at 8%, the dehydration residence time is 15 min; the dehydrated material is pressurized to 25 MPa by the pump 48, and the material is sent to the preheater (heat exchanger) 49 for preheating to 330 ° C, in the prepolymerization reaction.
  • the reactor 50 is kept at 330 ° C for 2.5 min; the prepolymerized reaction solution is depressurized to 0.3 MPa through a pressure reducing valve 51, and then enters the flasher 52. The flashed molten liquid material is depressurized to normal pressure and then enters the twin-screw extruder 54.
  • the reaction temperature is 330-340 ° C, the reaction residence time is 2 min;
  • the reacted material was granulated in an underwater granulator 55 and dried by a dryer 56 to obtain a semi-aromatic polyamide product having an IV of 0.83 dL/g and a gel content of 1.60% at about 12.2 kg/h. .
  • the semi-aromatic polyamide having a low gel content can be obtained by the method of the present invention.
  • the steam generated by the dehydration process is used for heating in the salt-forming process, the energy consumption of the process can be reduced; the excess water vapor can be combined with the condensed water generated in the heating process after condensation to be used as supplementary water for formation. The process of the slurry, thereby reducing the discharge of process wastewater.
  • the present invention adopts multi-channel on-line Raman spectroscopy, and according to the characteristic Raman absorption peak of different raw materials, continuously quantitatively determines the content of each component when the ratio of amine to acid is less than 1.0, so that the proportion of raw materials can be continuously adjusted in the production process to achieve continuous produce.

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Abstract

一种半芳香族聚酰胺生产方法及半芳香族聚酰胺，所述半芳香族聚酰胺生产方法包括：步骤1，将二元胺与二元酸按照胺酸摩尔比小于1.0的初始投料，与水、及催化剂形成浆料，浆料经升温、溶解形成盐溶液；步骤2，检测所述盐溶液的组成之后，将所述盐溶液脱水，检测脱水装置中出来的蒸汽冷凝水中的二元胺的含量，用熔融二元胺和分子量调节剂一元酸调整胺酸摩尔比至大于1.0，进行预聚反应；步骤3，预聚反应液经减压闪蒸后进行后缩聚反应。该方法制备的半芳香族聚酰胺产品凝胶含量低，性能优异，适用领域广泛。

Description

[根据细则37.2由ISA制定的发明名称]　半芳香族聚酰胺生产方法及半芳香族聚酰胺 技术领域
本发明涉及一种半芳香族聚酰胺生产方法以及半芳香族聚酰胺，尤其涉及低凝胶半芳香族聚酰胺的连续生产方法。
背景技术
半芳香族聚酰胺通常是由芳香族二元酸、脂肪族的二酸与脂肪族二元胺经缩聚反应得到的带苯环结构的聚酰胺。由于在主链中导入了芳环结构，半芳香族聚酰胺具有较好的耐热性能和力学性能，较低的吸水率，并具有较合适的性价比，填补了通用工程塑料尼龙和耐高温工程塑料PEEK之间的空白，可应用于电子、电器、汽车、服装纤维等领域。
半芳香族聚酰胺的制备通常采用预聚-后缩聚反应工艺。其中预聚反应通常以水为反应溶剂，先将二元酸和二元胺在成盐釜中进行中和反应形成盐溶液，然后再升温到一定温度进行脱水、预聚反应，得到预聚体水溶液，将预聚体水溶液减压闪蒸得到预聚体固体或融体；将预聚体进一步进行固相或熔融后缩聚反应即可得到一定分子量的半芳香族聚酰胺产品。为稳定产品质量，一般希望采用连续化生产工艺。
在US4603166、US4603193、US4617342中，介绍了将芳香族二元酸、脂肪族二元酸、脂肪族二元胺、催化剂、分子量调节剂一起先分批成盐，然后再连续进行预聚反应、闪蒸、熔融后缩聚反应合成半芳香族聚酰胺的方法。该法在预聚反应时采用高温、短停留时间，闪蒸后物料直接进行熔融后缩聚，提高了生产效率。
在CN105377948A中，介绍了将不同比例的对苯二甲酸与间苯二甲酸、脂肪族二元胺、催化剂、分子量调节剂一起先分批成盐，然后再连续进行预 聚反应、闪蒸及熔融后缩聚反应合成半芳香族聚酰胺的方法。该法在预聚反应后的物料直接闪蒸得到预聚体，预聚体直接进行熔融后缩聚得到半芳香族聚酰胺。该法为弥补闪蒸时二元胺的损失，需要在成盐过程中有较高的胺酸比。
在CN1678660A中，介绍了一种连续化生产聚酰胺的工艺，当生产半芳香族聚酰胺时，是将芳香族二元酸、脂肪族二元酸、脂肪族二元胺、催化剂、分子量调节剂一起先分批成盐，然后再经连续管道预聚反应、釜式脱水预聚反应、熔融后缩聚反应得到产品。该法在预聚反应后物料直接进行熔融后缩聚，同时根据熔融缩聚反应器出口粘度调节封端剂的量，以达到稳定聚酰胺粘度的目的。
在CN1166844A中，介绍了一种连续化生产聚酰胺的工艺，是采用以脂肪族二元酸为主的熔融富酸组分从垂直多段反应器的顶部进入、脂肪族二元胺蒸汽在垂直多段反应器的下部进入，在反应器中进行逆流连续缩聚反应制备聚酰胺的方法。该法在反应器出口附近装有近红外分析仪器，可以在线分析端胺基和端羧基比例，并据此进行物料配比的调整。由于进料必须是熔融态的，因此该法主要用于尼龙6,6的制备，对芳香族二元酸含量超过50％的半芳香族聚酰胺也不合适。
综上所述，现有半芳香族聚酰胺生产工艺中还存在以下问题：
(1)由于芳香族二元酸熔点超过其分解温度，因此，现有文献报道的工艺中，成盐反应都是分批进行的，每批盐溶液中二元酸与二元胺的比例都需要取样分析测定，然后根据测定结果进行调节，这使得预聚反应无法实现真正的连续化。
(2)现有的在线测试方法只能定量分析端羧基和端胺基含量，无法分析原料的组成，因此，无法实现投料过程的自动控制。
(3)对脱水过程中损失的胺、酸无法连续定量，因此，无法根据脱水物料的实际胺酸比进行自动调节，以稳定预聚反应。
(4)根据预聚或缩聚反应出口的端基含量进行调节的滞后时间长，调节过程中胺酸比容易产生波动。而胺酸比过高容易产生凝胶化副反应，从而降低产品的品质。
发明内容
发明要解决的问题
针对上述问题，本发明提供一种聚酰胺生产方法以及低凝胶含量的聚酰胺，尤其是提供一种连续化低凝胶含量半芳香族聚酰胺的生产方法。
用于解决问题的方案
本发明的第一方面提供一种半芳香族聚酰胺生产方法，其包括：
步骤1，将二元胺与二元酸按照胺酸摩尔比小于1.0的初始投料，与水、及催化剂形成浆料，浆料经升温、溶解形成盐溶液，
步骤2，检测所述盐溶液的组成之后，将所述盐溶液脱水，检测脱水装置中出来的蒸汽冷凝水中的二元胺的含量，用二元胺和分子量调节剂一元酸调整胺酸摩尔比至大于1.0，进行预聚反应，
步骤3，预聚反应液经减压闪蒸后进行后缩聚反应。
根据上述方法，所述步骤1中初始投料的胺酸摩尔比为0.90-0.99，优选为0.92-0.98。
根据上述方法，所述二元酸包括芳香族二元酸、脂肪族二元酸，所述芳香族二元酸与脂肪族二元酸的摩尔比为100：0～40：60，优选为100：0～50：50。
根据上述方法，所述脂肪族二元酸选自丁二酸、戊二酸、己二酸、辛二 酸、壬二酸、癸二酸、十二烷二酸中的一种或几种，所述芳香族二元酸选自间苯二甲酸、对苯二甲酸、萘二甲酸中的一种或几种。
根据上述方法，所述二元胺选自己二胺、庚二胺、辛二胺、壬二胺、癸二胺、2-甲基戊二胺、十一亚甲基二胺、十二亚甲基二胺、苯二亚甲基二胺中的一种或几种，优选所述二元胺选自己二胺、辛二胺、癸二胺中的一种或几种。
根据上述方法，所述分子量调节剂一元羧酸选自乙酸、丙酸、丁酸、戊酸、己酸、辛酸、癸酸、月桂酸、棕榈酸、软脂酸、硬脂酸、苯甲酸或苯乙酸中的一种或几种。
根据上述方法，所述分子量调节剂一元酸的摩尔数相对于初始投料中二元酸的总摩尔数为0.1-5％，优选为0.5-3％。
根据上述方法，所述催化剂的质量相对于初始投料中二元酸的总质量为0.01-2.5％。
根据上述方法，所述步骤1中还包括：检测所述盐溶液中二元酸的组成，通过添加芳香族二元酸和/或脂肪族二元酸以维持二元酸组成稳定的步骤。
根据上述方法，所述步骤1中的检测采用在线拉曼光谱。
根据上述方法，所述步骤2中的检测采用在线拉曼光谱。
根据上述方法，所述步骤2中的胺酸摩尔比为1.005-1.05，优选为1.01-1.04。
根据上述方法，脱水的温度为170-260℃，压力为0.7-2.0MPa，脱水时间为10-40min。
根据上述方法，所述预聚反应的温度为250-350℃，压力为10-30MPa，反应时间为1-15min。
根据上述方法，所述后缩聚反应的反应温度为300-350℃，反应时间为 0.5-5min。
根据上述方法，所述步骤2中脱水工序产生的水蒸汽可作为热源用于浆料的升温、溶解，多余水蒸汽可在冷凝后与升温工序中产生的冷凝水合并作为补加水用于形成浆料的工序。
本发明的第二方面提供一种半芳香族聚酰胺，其根据上述方法制备得到，其凝胶含量为1.0％以下，优选为0.8％以下。
本发明的第三方面提供一种半芳香族聚酰胺，其通过二元酸与脂肪族二元胺经缩聚反应而得到，所述二元酸包括芳香族二元酸、脂肪族二元酸，所述芳香族二元酸与脂肪族二元酸的摩尔比为100：0～40：60，优选为100：0～50：50；其凝胶含量为1.0％以下，优选为0.8％以下。
根据上述的半芳香族聚酰胺，所述脂肪族二元酸选自丁二酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、十二烷二酸中的一种或几种，所述芳香族二元酸选自间苯二甲酸、对苯二甲酸、萘二甲酸中的一种或几种。
根据上述的半芳香族聚酰胺，所述二元胺选自己二胺、庚二胺、辛二胺、壬二胺、癸二胺、2-甲基戊二胺、十一亚甲基二胺、十二亚甲基二胺、苯二亚甲基二胺中的一种或几种，优选所述二元胺选自己二胺、辛二胺、癸二胺中的一种或几种。
根据上述的半芳香族聚酰胺，所述半芳香族聚酰胺的特性粘度为0.7～1.0dl/g。
发明的效果
本发明人的研究表明，在半芳香族聚酰胺的生产方法中，于形成浆料、溶解成盐、脱水工序保证体系中胺酸摩尔比小于1.0，并适当控制脱水、预聚、后缩聚反应的时间，可以降低凝胶化程度。在本发明的某一具体实施方案中， 所得半芳香族聚酰胺的凝胶量低，流动性好，机械强度高，可适应不同后加工过程的要求。
在本发明的具体实施方案中，将脱水工序产生的蒸汽用于溶解成盐过程的加热，可降低过程的能耗；多余的水蒸汽可在冷凝后与升温工序中产生的冷凝水合并作为补加水用于形成浆料的工序，从而减少过程废水的排放。
在本发明的具体实施方案中，通过在线检测脱水前的盐溶液中的组成(包括胺酸摩尔比)和脱水装置中出来的蒸汽冷凝水中的二元胺的含量，可以根据实际情况在生产过程中调整各原料的比例。比如，根据拉曼光谱检测结果采用熔融脂肪族二元酸及芳香族二元酸浆料与熔融二元胺可对反应物料组成进行连续微调，从而实现了生产过程的完全连续化；而将分子量调节剂在脱水以后添加可以避免因脱水引起的损失，从而达到精确控制配比的目的。在本发明的一个具体实施方案中，采用多通道在线拉曼光谱，根据不同原料的特征拉曼吸收峰，连续定量测定胺酸比小于1.0时各组分的含量，从而可以在生产过程中连续调整原料比例、稳定生产过程。
本发明的具体实施方案中，生产过程可以完全连续化、能耗低；所得产品凝胶含量低，性能优异，适用领域广泛。
附图说明
图1显示各种尼龙盐的归一化拉曼光谱(600～1200cm-1)。
图2显示各种尼龙盐的归一化拉曼光谱(1200～1800cm-1)。
图3显示本发明实施例的工艺流程图。
图4显示比较例1～6的工艺流程图。
附图标记说明
1 脂肪酸二元酸料仓
2、4、6 进料螺杆输送器
3 对苯二甲酸料仓
5 间苯二甲酸(或其他二元酸)料仓
7 催化剂水溶液储罐
8、10、12、13、17、23、24、26、28、30、32 泵
9 打浆釜
11 熔融二元胺储罐
14 多级搅拌溶解釜
15、27、33、44、49 热交换器
16、18、20 在线拉曼光谱检测器
19 溶解成盐釜
21 控制器
22 熔融脂肪族二元酸储罐
25 间苯二甲酸(或其他二元酸)料浆储罐
29、46 脱水器
31 熔融一元酸储罐
34、50 预聚反应器
35、37、51、53 减压阀
36、52 闪蒸器
38、54 后缩聚反应器(双螺杆挤出机)
39、55 造粒机
40、56 干燥机
41、42 成盐釜
43 盐溶液输送泵
45 循环泵
47 冷凝器
48 脱水物料进料泵
具体实施方式
本发明的第一方面是提供一种半芳香族聚酰胺生产方法，其包括：
步骤1，将二元胺与二元酸按照胺酸摩尔比小于1.0的初始投料，与水、及催化剂形成浆料，浆料经升温、溶解形成盐溶液，
步骤2，检测所述盐溶液的组成之后，将所述盐溶液脱水，检测脱水装置中出来的蒸汽冷凝水中的二元胺的含量，用熔融二元胺和分子量调节剂一元酸调整胺酸摩尔比至大于1.0，进行预聚反应，
步骤3，预聚反应液经减压闪蒸后进行后缩聚反应。
所述二元酸包括芳香族二元酸、脂肪族二元酸，二者的摩尔比为100：0～40：60，优选为100：0～50：50。
所述脂肪族二元酸选自丁二酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、十二烷二酸中的一种或几种，优选己二酸、辛二酸、癸二酸、十二烷二酸中的一种或几种；所述芳香族二元酸选自间苯二甲酸、对苯二甲酸、萘二甲酸中的一种或几种，优选间苯二甲酸、对苯二甲酸中的一种或几种。
所述二元胺选自己二胺、庚二胺、辛二胺、壬二胺、癸二胺、2-甲基戊二胺、十一亚甲基二胺、十二亚甲基二胺、苯二亚甲基二胺中的一种或几种，优选所述二元胺选自己二胺、辛二胺、癸二胺中的一种或几种。
所述分子量调节剂一元酸选自乙酸、丙酸、丁酸、戊酸、己酸、辛酸、癸酸、月桂酸、棕榈酸、软脂酸、硬脂酸、苯甲酸或苯乙酸中的一种或几种，所加入的分子量调节剂的摩尔量为原料二羧酸总摩尔量的0.1-5％，优选为0.5-3％。
所述初始投料胺酸摩尔比小于1.0，优选初始投料时胺酸摩尔比为 0.90-0.99，更优选初始投料胺酸摩尔比为0.92-0.98。
所述半芳香族聚酰胺生产方法可采用磷基化合物作为催化剂。磷基化合物包括，例如，磷酸、亚磷酸、次磷酸和其盐或酯衍生物，如磷酸、亚磷酸或次磷酸，或者磷酸、亚磷酸或次磷酸金属的钠、钾、镁、钒、钙、锌、钴、锰、锡、钨、锗、钛或锑盐；磷酸铵，亚磷酸铵和连二磷酸铵；磷酸、亚磷酸或次磷酸的乙基酯、异丙基酯、丁基酯、己基酯、异癸基酯、十八烷基酯、癸基酯、十八酰基酯或苯基酯。
所述催化剂优选为选自磷酸钠、磷酸钾、亚磷酸钠、亚磷酸钾、次磷酸钠、次磷酸钾中的一种或几种。所述催化剂的质量相对于初始投料中二元酸的总质量为0.01-2.5％，优选为0.05-1％。
在本发明的一个具体实施方案中，所述步骤1中还包括：检测所述盐溶液中二元酸的组成，通过添加芳香族二元酸和/或脂肪族二元酸以维持二元酸组成稳定的步骤。比如，采用在线拉曼光谱检测得到盐溶液中二元酸的组成，根据检测结果，采用熔融脂肪族二元酸和/或芳香族二元酸浆料来调节盐溶液中的二元酸的组成，使之维持稳定。
在本发明的一个具体实施方案中，通过在线拉曼光谱检测脱水前的盐溶液中的胺酸摩尔比和脱水装置中出来的蒸汽冷凝水中的二元胺的含量，根据检测结果，用二元胺和分子量调节剂一元酸调整胺酸摩尔比至大于1.0。所述用二元胺和分子量调节剂一元酸调整胺酸摩尔比至大于1.0是指调整后的脂肪族二元胺与脂肪族二元酸、芳香族二元酸和分子量调节剂一元酸之和的胺酸摩尔比控制在大于1.0，优选为1.005-1.05，更优选为1.01-1.04。
在本发明的一个具体实施方案中，提供一种半芳香族聚酰胺的生产方法，进一步地，提供一种半芳香族聚酰胺的连续生产方法。比如，采用在线拉曼光谱检测得到盐溶液中二元酸的组成，根据检测结果，采用熔融脂肪族二元酸和/或芳香族二元酸浆料来调节盐溶液中的二元酸的组成，使之维持稳定。并且，通过在线拉曼光谱检测脱水前的物料中的胺酸摩尔比和脱水装置 中出来的蒸汽冷凝水中的二元胺的含量，根据检测结果，用二元胺和分子量调节剂一元酸调整胺酸摩尔比至大于1.0。
脱水阶段脱出的水蒸汽可作为热源用于浆料的升温溶解过程，多余的水蒸汽可在冷凝后与升温工序中产生的冷凝水合并作为补加水用于形成浆料的工序。
在本发明的一个具体实施方案中，在形成浆料工序中，体系的含水量可以为10-50％，优选为15-30％，温度可以为50-95℃，优选为60-90℃。溶解成盐的温度可以为120-170℃，优选为130-160℃。在脱水工序中，脱水的温度可以为170-260℃，优选为190-240℃；压力可以为0.7-2.0MPa，优选为1.0-1.8MPa；脱水时间可以为10-40min，优选为15-30min；脱水后的含水量为5-20％，优选为7-15％。
在本发明的一个具体实施方案中，预聚反应温度可以为250-350℃，优选为280-340℃；压力可以为10-30MPa，优选为15-25MPa；反应时间可以为1-15min，优选为2-10min。预聚反应后减压闪蒸压力可以为0.15-0.9MPa，优选为0.2-0.6MPa，温度可以与预聚反应的温度相同。闪蒸后预聚体以熔体方式进入双螺杆挤出机，进行后缩聚反应，反应温度可以为300-350℃，优选为310-340℃；反应时间可以为0.5-5min，优选为1-3min。
在本发明的一个具体实施方案中，将初始投料胺酸摩尔比小于1.0的二元胺与脂肪族二元酸、芳香族二元酸，和水及催化剂一起连续打浆形成浆料，浆料经预热器用脱水过程产生的蒸汽加热升温、溶解成盐。使盐溶液进入脱水器进行升温、脱水，脱水前的物料经在线拉曼光谱检测，再结合脱水过程中蒸汽冷凝水中二元胺的在线拉曼光谱分析结果，用熔融二元胺和分子量调节剂一元酸调整胺酸摩尔比至1.005-1.05；然后进入到预聚反应器进行升温预聚反应。预聚反应液经减压闪蒸后进入双螺杆挤出机进行后缩聚反应，再经水下造粒、干燥得到低凝胶半芳香族聚酰胺产品。
本发明的第二方面是提供一种半芳香族聚酰胺，其凝胶含量为1.0％以下，优选为0.8％以下，更优选为0.5％以下，最优选为0.3％以下。所述半芳香族聚酰胺，其采用本发明第一方面提供的生产方法制备。
本发明的第三方面是提供一种半芳香族聚酰胺，其通过二元酸与脂肪族二元胺经缩聚反应而得到，所述二元酸包括芳香族二元酸、脂肪族二元酸，所述芳香族二元酸与脂肪族二元酸的摩尔比为100：0～40：60，优选为100：0～50：50；其凝胶含量为1.0％以下，优选为0.8％以下，更优选为0.5％以下，最优选为0.3％以下。
半芳香族聚酰胺的特性粘度[η]优选为0.7～1.0dL/g。如果特性粘度[η]在上述的范围内，则可以改善含有上述的半芳香族聚酰胺的树脂组合物的成型时的流动性，且获得的成型物的机械特性也变好。此外，如果半芳香族聚酰胺的特性粘度[η]过低，则含有其的树脂组合物的熔融张力容易变得比期望的范围低。
实施例：
为了使本技术领域的技术人员能够更好地理解本发明的技术方案，下面结合实施例，进一步阐述本发明。但应当理解的是，所述实施例仅是本发明的具体方案，不应将其理解为对本发明的限制。实施例中的百分数，如果没有特殊规定，则为质量百分数。在实施例和比较例中的诸特性，均是按以下方法测定的。
1、特性粘度(Intrinsic Viscosity)
将样品溶解在苯酚-四氯乙烷(质量比3:2)的混合溶剂中，得到浓度为0.1、0.5、1.0g/dL的溶液，在30℃的恒温水浴环境中，用乌氏粘度计测量样品溶液的比浓对数粘数ηln。
ηln＝[ln(t/t0)]/C(dL/g)
其中t0为溶剂的流经时间(秒)，t为溶液的流经时间(秒)，C为样品溶液的浓度(g/dL)。
将ηln的数据外推到浓度为0，即可得到样品的特性粘度[η]。
2、凝胶含量的检测
首先称取0.25g聚合物，放入25ml容量瓶中，加入约20ml98％的浓硫酸，然后将容量瓶置于50℃水浴的摇床中溶解1h。取出容量瓶，将瓶中溶液采用G2型号砂芯漏斗过滤至烧杯中，将所得滤液缓缓倒入水中，并不断搅拌使聚合物析出，过滤出聚合物，并用水洗涤，干燥，称重。
凝胶含量＝(处理前聚合物重量-处理后聚合物重量)/处理前聚合物重量*100％
3、拉曼光谱
通过对对苯二甲酸(TA)、间苯二甲酸(IA)、己二酸(AA)、己二胺(HDA)混合成盐后拉曼光谱(附图1、2)的分析研究，本发明采用以下拉曼光谱信息确定各组分的含量：
(1)间苯二甲酸(IA)及其盐(6I)的含量由位于1005cm-1和762cm-1的特征峰确定；
(2)对苯二甲酸(TA)及其盐(6T)的含量由位于1128cm-1和854cm-1的特征峰确定；
(3)已二酸(AA)及其盐(66)的含量由位于920cm-1和936cm-1的特征峰确定；
(4)已二胺(HDA)的含量由位于1485cm-1的特征峰确定。
实施例1-6均按附图3流程进行实施；比较例均按附图4流程进行实施。生产过程中，所有物料均采用高纯氮气进行脱氧处理，生产过程的所有装置 均由高纯氮气置换并保护。
实施例1
按初始投料胺酸摩尔比0.95的比例，将4.15Kg/h(25mol/h)对苯二甲酸、3.65Kg/h(25mol/h)己二酸、5.51Kg/h(47.5Kmol/h)己二胺、0.04Kg/h的20％次磷酸钠水溶液与3.2Kg/h的水一起投入打浆釜9中，于60℃连续打浆形成浆料。浆料经泵10输送到多级搅拌溶解釜14中用脱水过程中产生的蒸汽加热升温至150℃溶解成盐。根据在线拉曼光谱18检测盐溶液中二元酸的组成，通过计量泵23采用熔融己二酸调节脂肪族二元酸的量，使溶解成盐釜19中芳香族二元酸与脂肪族二元酸的比例维持稳定。上述盐溶液经在线拉曼光谱20检测组成后，由泵24增压到1.2MPa后输送到脱水器的预热器(热交换器)27之前与循环泵28输送的物料混合后进行升温，在脱水器29中脱水，脱水温度控制在190℃，含水量控制在15％，脱水停留时间为30min。脱水器出来的蒸汽作为多级搅拌溶解釜14的热源，通过热交换器15冷却后，由在线拉曼光谱16检测其中的胺含量。结合拉曼光谱16及20的检测结果，通过控制器21确定泵32之前所需补充熔融己二胺的量；脱水合格的物料分别通过泵17、泵30用熔融己二胺和0.06Kg/h(1mol/h)分子量调节剂乙酸调整胺酸摩尔比至1.01。然后用泵32增压到10MPa，将物料输送到预热器(热交换器)33中预热升温到280℃，在预聚反应器34中于280℃保温反应5min；预聚反应液经减压阀35减压到0.2MPa后进入闪蒸器36中。闪蒸后熔融液体物料经减压阀37减压到常压后进入双螺杆挤出机38中进行后缩聚反应，反应温度300-310℃，反应停留时间5min。经后缩聚反应的物料在水下造粒机39中进行造粒，再经干燥机40干燥，以约11.8Kg/h得到低凝胶半芳香族聚酰胺产品，其特性粘度IV为0.92dL/g，凝胶量为0.21％。
实施例2
按初始投料胺酸摩尔比0.92的比例，将3.32Kg/h(20mol/h)对苯二甲酸、6.06Kg/h(30mol/h)癸二酸、7.91Kg/h(46mol/h)癸二胺、0.47Kg/h的20％次磷酸钾水溶液与5.46Kg/h的水一起投入打浆釜9中，于70℃连续打浆形成浆料。浆料经泵10输送到多级搅拌溶解釜14中，用脱水过程中产生的蒸汽加热升温至160℃溶解成盐，根据在线拉曼光谱18检测盐溶液中二元酸的组成。通过计量泵23采用熔融癸二酸调节脂肪族二元酸的量，使溶解成盐釜19中芳香族二元酸与脂肪族二元酸的比例维持稳定。上述盐溶液经在线拉曼光谱20检测组成后，由泵24增压到1.8MPa后输送到脱水器的预热器(热交换器)27之前与循环泵28输送的物料混合后进行升温，在脱水器29中脱水，脱水温度控制在240℃，含水量控制在7％，脱水停留时间为15min。脱水器出来的蒸汽作为多级搅拌溶解釜14的热源，通过热交换器15冷却后由在线拉曼光谱16检测其中的胺含量。结合拉曼光谱16及20的检测结果，通过控制器21确定泵32之前所需补充熔融癸二胺的量。脱水合格的物料分别通过泵17、泵30用熔融癸二胺和0.34Kg/h(2mol/h)分子量调节剂癸酸调整胺酸摩尔比至1.02，然后用泵32增压到25MPa，将物料输送到预热器(热交换器)33中预热升温到340℃，在预聚反应器34中于340℃保温反应2min。预聚反应液经减压阀35减压到0.6MPa后进入闪蒸器36中，闪蒸后熔融液体物料经减压阀37减压到常压后进入双螺杆挤出机38中进行后缩聚反应，反应温度320-330℃，反应停留时间3min。经后缩聚反应的物料在水下造粒机39中进行造粒，再经干燥机40干燥，以约16.7Kg/h得到低凝胶半芳香族聚酰胺产品，其IV为0.78dL/g，凝胶量为0.23％。
实施例3
按初始投料胺酸摩尔比0.98的比例，将6.64Kg/h(40mol/h)对苯二甲酸、2.30Kg/h(10mol/h)十二烷二酸、5.68Kg/h(49mol/h)己二胺、0.2Kg/h的20％亚磷酸钠水溶液与2.42Kg/h水一起投入打浆釜9中，于60℃连续打浆形成浆料。浆料经泵10输送到多级搅拌溶解釜14中用脱水过程中产生的蒸汽加热升温至160℃溶解成盐。根据在线拉曼光谱18检测盐溶液中二元酸的组成，通过计量泵23采用熔融十二烷二酸调节脂肪族二元酸的量，使溶解成盐釜19中芳香族二元酸与脂肪族二元酸的比例维持稳定。上述盐溶液经在线拉曼光谱20检测组成后，由泵24增压到1.5MPa后输送到脱水器的预热器(热交换器)27之前与循环泵28输送的物料混合后进行升温，在脱水器29中脱水，脱水温度控制在220℃，脱水停留时间为20min。脱水器出来的蒸汽作为多级搅拌溶解釜14的热源，通过热交换器15冷却后，由在线拉曼光谱16检测其中的胺含量。结合拉曼光谱16及20的检测结果，通过控制器21确定泵32之前所需补充熔融己二胺的量；脱水合格的物料分别通过泵17、泵30用熔融己二胺和0.27Kg/h(2mol/h)分子量调节剂苯乙酸调整胺酸摩尔比至1.04。然后用泵32增压到20MPa，将物料输送到预热器(热交换器)33中预热升温到320℃，在预聚反应器34中于320℃保温反应3min；预聚反应液经减压阀35减压到0.4MPa后进入闪蒸器36中，闪蒸后熔融液体物料经减压阀37减压到常压后进入双螺杆挤出机38中进行后缩聚反应，反应温度310-320℃，反应停留时间4min。经后缩聚反应的物料在水下造粒机39中进行造粒，再经干燥机40干燥，以约13.2Kg/h得到低凝胶半芳香族聚酰胺产品，其IV为0.72dL/g，凝胶量为0.20％。
实施例4
按初始投料胺酸摩尔比0.90的比例，将4.98Kg/h(30mol/h)间苯二甲酸、 3.48Kg/h(20mol/h)辛二酸、9.0Kg/h(45mol/h)十二亚甲基二胺、0.15Kg/h的20％次磷酸钾水溶液与7.64Kg/h的水一起投入打浆釜9中，于50℃连续打浆形成浆料。浆料经泵10输送到多级搅拌溶解釜14中用脱水过程中产生的蒸汽加热升温至130℃溶解成盐。根据在线拉曼光谱18检测盐溶液中二元酸的组成。通过计量泵23采用熔融辛二酸调节脂肪族二元酸的量，使溶解成盐釜19中芳香族二元酸与脂肪族二元酸的比例维持稳定。上述盐溶液经在线拉曼光谱20检测组成后，由泵24增压到0.7MPa后输送到脱水器的预热器(热交换器)27之前与循环泵28输送的物料混合后进行升温，在脱水器29中脱水，脱水温度控制在170℃，含水量控制在20％，脱水停留时间为30min。脱水器出来的蒸汽作为多级搅拌溶解釜14的热源，通过热交换器15冷却后由在线拉曼光谱16检测其中的胺含量。结合拉曼光谱16及20的检测结果，通过控制器21确定泵32之前所需补充熔融十二亚甲基二胺的量。脱水合格的物料分别通过泵17、泵30用熔融十二亚甲基二胺和0.05Kg/h(0.25mol/h)分子量调节剂月桂酸调整胺酸摩尔比至1.005，然后用泵32增压到30MPa，将物料输送到预热器(热交换器)33中预热升温到330℃，在预聚反应器34中于330℃保温反应3min；预聚反应液经减压阀35减压到0.15MPa后进入闪蒸器36中，闪蒸后熔融液体物料经减压阀37减压到常压后进入双螺杆挤出机38中进行后缩聚反应，反应温度340-350℃，反应停留时间0.5min。经后缩聚反应的物料在水下造粒机39中进行造粒，再经干燥机40干燥，以约16.7Kg/h得到低凝胶半芳香族聚酰胺产品，其IV为0.98dL/g，凝胶量为0.27％。
实施例5
按初始投料胺酸摩尔比0.99的比例，将5.40Kg/h(25mol/h)萘二甲酸、2.95Kg/h(25mol/h)丁二酸、5.74Kg/h(49.5mol/h)2-甲基戊二胺、0.25Kg/h10％ 次磷酸钠与10％磷酸钠的混合水溶液和13.9Kg/h水一起投入打浆釜9中，于95℃连续打浆形成浆料。浆料经泵10输送到多级搅拌溶解釜14中用脱水过程中产生的蒸汽加热升温至170℃溶解成盐，根据在线拉曼光谱18检测盐溶液中二元酸的组成。通过计量泵23采用熔融丁二酸调节脂肪族二元酸的量，使溶解成盐釜19中芳香族二元酸与脂肪族二元酸的比例维持稳定。上述盐溶液经在线拉曼光谱20检测组成后，由泵24增压到2.0MPa后输送到脱水器的预热器(热交换器)27之前与循环泵28输送的物料混合后进行升温，在脱水器29中脱水，脱水温度控制在260℃，含水量控制在5％，脱水停留时间为10min。脱水器出来的蒸汽作为多级搅拌溶解釜14的热源，通过热交换器15冷却后由在线拉曼光谱16检测其中的胺含量。结合拉曼光谱16及20的检测结果，通过控制器21确定泵32之前所需补充熔融2-甲基戊二胺的量。脱水合格的物料分别通过泵17、泵30用熔融2-甲基戊二胺和0.22Kg/h(2.5mol/h)分子量调节剂丁酸调整胺酸摩尔比至1.05。然后用泵32增压到27MPa，将物料输送到预热器(热交换器)33中预热升温到320℃，在预聚反应器34中于320℃保温反应3min。预聚反应液经减压阀35减压到0.9MPa后进入闪蒸器36中，闪蒸后熔融液体物料经减压阀37减压到常压后，进入双螺杆挤出机38中进行后缩聚反应，反应温度320-330℃，反应停留时间3min。经后缩聚反应的物料在水下造粒机39中进行造粒，再经干燥机40干燥，以约12.5Kg/h得到低凝胶半芳香族聚酰胺产品，其IV为0.72dL/g，凝胶量为0.25％。
实施例6
按初始投料胺酸摩尔比0.96的比例，将预先混合均匀的5.81Kg/h(35mol/h)对苯二甲酸、2.49Kg/h(15mol/h)间苯二甲酸、5.57Kg/h(48mol/h)己二胺、0.15Kg/h的20％次磷酸钠水溶液与6.5Kg/h水一起投入打浆釜9中， 于70℃连续打浆形成浆料。浆料经泵10输送到多级搅拌溶解釜14中用脱水过程中产生的蒸汽加热升温至165℃溶解成盐，根据在线拉曼光谱18检测盐溶液中二元酸的组成。通过计量泵26采用50％间苯二甲酸浆料调节间苯二甲酸的量，使溶解成盐釜19中对苯二甲酸与间苯二甲酸的比例维持稳定。上述盐溶液经在线拉曼光谱20检测组成后，由泵24增压到1.8MPa后输送到脱水器的预热器(热交换器)27之前与循环泵28输送的物料混合后进行升温，在脱水器29中脱水，脱水温度控制在235℃，含水量控制在8％，脱水停留时间为15min。脱水器出来的蒸汽作为多级搅拌溶解釜14的热源，通过热交换器15冷却后由在线拉曼光谱16检测其中的胺含量。结合拉曼光谱16及20的检测结果，通过控制器21确定泵32之前所需补充熔融己二胺的量。脱水合格的物料分别通过泵17、泵30用熔融己二胺和0.11Kg/h(1.5mol/h)分子量调节剂丙酸调整胺酸摩尔比至1.025，然后用泵32增压到25MPa，将物料输送到预热器(热交换器)33中预热升温到330℃，在预聚反应器34中于330℃保温反应2.5min。预聚反应液经减压阀35减压到0.3MPa后进入闪蒸器36中，闪蒸后熔融液体物料经减压阀37减压到常压后进入双螺杆挤出机38中进行后缩聚反应，反应温度330-340℃，反应停留时间2min。经后缩聚反应的物料在水下造粒机39中进行造粒，再经干燥机40干燥，以约12.4Kg/h得到低凝胶半芳香族聚酰胺产品，其IV为0.77dL/g，凝胶量为0.20％。
比较例1
按初始投料胺酸摩尔比1.01的比例，将33.2Kg(200mol)对苯二甲酸、29.2Kg(200mol)己二酸、44.1Kg(408mol)己二胺、0.31Kg20％次磷酸钠水溶液、0.48Kg(8mol)分子量调节剂乙酸与25.6Kg水一起投入成盐釜41或42(每8小时切换一次)中升温至150℃溶解成盐，上述盐溶液以16.6Kg/h 流量由泵43增压到1.2MPa后输送到脱水器的预热器(热交换器)44之前与循环泵45输送的物料混合后进行升温，在脱水器46中脱水，脱水温度控制在190℃，含水量控制在15％，脱水停留时间为30min；脱水合格的物料用泵48增压到10MPa，将物料输送到预热器(热交换器)49中预热升温到280℃，在预聚反应器50中于280℃保温反应5min；预聚反应液经减压阀51减压到0.2MPa后进入闪蒸器52中，闪蒸熔融液体物料减压到常压后进入双螺杆挤出机54中进行后缩聚反应，反应温度300-310℃，反应停留时间5min；经后缩聚反应的物料在水下造粒机55中进行造粒，再经干燥机56干燥，以约11.6Kg/h得到半芳香族聚酰胺产品，其IV为0.98dL/g，凝胶量为1.03％。
比较例2
按初始投料胺酸摩尔比1.02的比例，将26.6Kg(160mol)对苯二甲酸、48.5Kg(240mol)癸二酸、71.6Kg(416mol)癸二胺、3.75Kg20％次磷酸钾水溶液、2.75Kg(16mol)分子量调节剂癸酸与43.7Kg水一起投入成盐釜41或42中(每8小时切换一次)升温至160℃溶解成盐；上述盐溶液以24.0Kg/h流量由泵43增压到1.8MPa后输送到脱水器的预热器(热交换器)44之前与循环泵45输送的物料混合后进行升温，在脱水器46中脱水，脱水温度控制在240℃，含水量控制在7％，脱水停留时间为15min；脱水合格的物料用泵48增压到25MPa，将物料输送到预热器(热交换器)49中预热升温到340℃，在预聚反应器50中于340℃保温反应2min；预聚反应液经减压阀51减压到0.6MPa后进入闪蒸器52中，闪蒸熔融液体物料减压到常压后进入双螺杆挤出机54中进行后缩聚反应，反应温度320-330℃，反应停留时间3min；经后缩聚反应的物料在水下造粒机55中进行造粒，再经干燥机56干燥，以约16.6Kg/h得到半芳香族聚酰胺产品，其IV为0.81dL/g，凝胶量为1.12％。
比较例3
按初始投料胺酸摩尔比1.04的比例，将53.1Kg(320mol)对苯二甲酸、18.4Kg(80mol)十二烷二酸、49.2Kg(424mol)己二胺、1.6Kg20％亚磷酸钠水溶液、2.18Kg(16mol)分子量调节剂苯乙酸与19.4Kg水一起投入成盐釜41或42(每8小时切换一次)中加热升温至160℃溶解成盐；上述盐溶液以18.0Kg/h流量由泵43增压到1.5MPa后输送到脱水器的预热器(热交换器)44之前与循环泵45输送的物料混合后进行升温，在脱水器46中脱水，脱水温度控制在220℃，脱水停留时间为20min；脱水合格的物料用泵48增压到20MPa，将物料输送到预热器(热交换器)49中预热升温到320℃，在预聚反应器50中于320℃保温反应3min；预聚反应液经减压阀51减压到0.4MPa后进入闪蒸器52中，闪蒸熔融液体物料减压到常压后进入双螺杆挤出机54中进行后缩聚反应，反应温度310-320℃，反应停留时间4min；经后缩聚反应的物料在水下造粒机55中进行造粒，再经干燥机56干燥，以约13.0Kg/h得到半芳香族聚酰胺产品，其IV为0.78dL/g，凝胶量为2.51％。
比较例4
按初始投料胺酸摩尔比1.005的比例，将39.8Kg(240mol)间苯二甲酸、27.8Kg(160mol)辛二酸、80.6Kg(403mol)十二亚甲基二胺、1.2Kg的20％次磷酸钾水溶液、0.4Kg(2mol)分子量调节剂月桂酸与61.1Kg水一起投入成盐釜41或42(每8小时切换一次)中加热升温至130℃溶解成盐；上述盐溶液以26.4Kg/h流量由泵43增压到0.7MPa后输送到脱水器的预热器(热交换器)44之前与循环泵45输送的物料混合后进行升温，在脱水器46中脱水，脱水温度控制在170℃，含水量控制在20％，脱水停留时间为30min；脱水合格 的物料用泵48增压到30MPa，将物料输送到预热器(热交换器)49中预热升温到330℃，在预聚反应器50中于330℃保温反应3min；预聚反应液经减压阀51减压到0.15MPa后进入闪蒸器52中，闪蒸熔融液体物料减压到常压后进入双螺杆挤出机54中进行后缩聚反应，反应温度340-350℃，反应停留时间0.5min；经后缩聚反应的物料在水下造粒机55中进行造粒，再经干燥机56干燥，以约16.6Kg/h得到半芳香族聚酰胺产品，其IV为1.02dL/g，凝胶量为0.97％。
比较例5
按初始投料胺酸摩尔比1.05的比例，将43.2Kg(200mol)萘二甲酸、23.6Kg(200mol)丁二酸、49.9Kg(430mol)2-甲基戊二胺、2Kg10％次磷酸钠与10％磷酸钠的混合水溶液、1.76Kg(20mol)分子量调节剂丁酸和111.1Kg水一起投入成盐釜41或42(每8小时切换一次)中加热升温至170℃溶解成盐；上述盐溶液以28.9Kg/h流量由泵43增压到2.0MPa后输送到脱水器的预热器(热交换器)44之前与循环泵45输送的物料混合后进行升温，在脱水器46中脱水，脱水温度控制在260℃，含水量控制在5％，脱水停留时间为10min；脱水合格的物料用泵48增压到27MPa，将物料输送到预热器(热交换器)49中预热升温到320℃，在预聚反应器50中于320℃保温反应3min；预聚反应液经减压阀51减压到0.9MPa后进入闪蒸器52中，闪蒸熔融液体物料减压到常压后进入双螺杆挤出机54中进行后缩聚反应，反应温度320-330℃，反应停留时间3min；经后缩聚反应的物料在水下造粒机55中进行造粒，再经干燥机56干燥，以约12.4Kg/h得到半芳香族聚酰胺产品，其IV为0.79dL/g，凝胶量为2.35％。
比较例6
按初始投料胺酸摩尔比1.025的比例，将预先混合均匀的46.5Kg(280mol)对苯二甲酸、19.9Kg(120mol)间苯二甲酸、48.3Kg(416mol)己二胺、1.2Kg20％次磷酸钠水溶液、0.89Kg(12mol)分子量调节剂丙酸与52Kg水一起投入成盐釜41或42(每8小时切换一次)中加热升温至165℃溶解成盐；上述盐溶液以19.3Kg/h流量由泵43增压到1.8MPa后输送到脱水器的预热器(热交换器)44之前与循环泵45输送的物料混合后进行升温，在脱水器46中脱水，脱水温度控制在235℃，含水量控制在8％，脱水停留时间为15min；脱水合格的物料用泵48增压到25MPa，将物料输送到预热器(热交换器)49中预热升温到330℃，在预聚反应器50中于330℃保温反应2.5min；预聚反应液经减压阀51减压到0.3MPa后进入闪蒸器52中，闪蒸熔融液体物料减压到常压后进入双螺杆挤出机54中进行后缩聚反应，反应温度330-340℃，反应停留时间2min；经后缩聚反应的物料在水下造粒机55中进行造粒，再经干燥机56干燥，以约12.2Kg/h得到半芳香族聚酰胺产品，其IV为0.83dL/g，凝胶量为1.60％。
将本发明的实施例与比较例相比，可以明确，按照本发明的方法可以得到凝胶含量低的半芳香族聚酰胺。同时，由于本发明将脱水工序产生的蒸汽用于溶解成盐过程的加热，可降低过程的能耗；多余的水蒸汽可在冷凝后与升温工序中产生的冷凝水合并作为补加水用于形成浆料的工序，从而减少过程废水的排放。另外，本发明采用多通道在线拉曼光谱，根据不同原料的特征拉曼吸收峰，连续定量测定胺酸比小于1.0时各组分的含量，从而可以在生产过程中连续调整原料比例，实现连续生产。

Claims (17)

  1. 一种半芳香族聚酰胺生产方法，其特征在于，包括：
    步骤1，将二元胺与二元酸按照胺酸摩尔比小于1.0的初始投料，与水、及催化剂形成浆料，浆料经升温、溶解形成盐溶液，
    步骤2，检测所述盐溶液的组成之后，将所述盐溶液脱水，检测脱水装置中出来的蒸汽冷凝水中的二元胺的含量，用二元胺和分子量调节剂一元酸调整胺酸摩尔比至大于1.0，进行预聚反应，
    步骤3，预聚反应液经减压闪蒸后进行后缩聚反应。
  2. 根据权利要求1所述方法，其特征在于，所述步骤1中初始投料的胺酸摩尔比为0.90-0.99，优选为0.92-0.98。
  3. 根据权利要求1或2所述方法，其特征在于，所述二元酸包括芳香族二元酸、脂肪族二元酸，所述芳香族二元酸与脂肪族二元酸的摩尔比为100：0～40：60，优选为100：0～50：50。
  4. 根据权利要求3所述方法，其特征在于，所述脂肪族二元酸选自丁二酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、十二烷二酸中的一种或几种，所述芳香族二元酸选自间苯二甲酸、对苯二甲酸、萘二甲酸中的一种或几种。
  5. 根据权利要求1～4任一项所述方法，其特征在于，所述二元胺选自己二胺、庚二胺、辛二胺、壬二胺、癸二胺、2-甲基戊二胺、十一亚甲基二胺、十二亚甲基二胺、苯二亚甲基二胺中的一种或几种，优选所述二元胺选自己二胺、辛二胺、癸二胺中的一种或几种。
  6. 根据权利要求1～5任一项所述方法，其特征在于，所述分子量调节剂一元羧酸选自乙酸、丙酸、丁酸、戊酸、己酸、辛酸、癸酸、月桂酸、棕榈酸、软脂酸、硬脂酸、苯甲酸或苯乙酸中的一种或几种。
  7. 根据权利要求1～6任一项所述方法，其特征在于，所述分子量调节剂 一元酸的摩尔数相对于初始投料中二元酸的总摩尔数为0.1-5％，优选为0.5-3％。
  8. 根据权利要求1～7任一项所述方法，其特征在于，所述催化剂的质量相对于初始投料中二元酸的总质量为0.01-2.5％。
  9. 根据权利要求1～8任一项所述方法，其特征在于，所述步骤1中还包括：检测所述盐溶液中二元酸的组成，通过添加芳香族二元酸和/或脂肪族二元酸以维持二元酸组成稳定的步骤。
  10. 根据权利要求9所述方法，其特征在于，所述步骤1中的检测采用在线拉曼光谱。
  11. 根据权利要求1～10任一项所述方法，其特征在于，所述步骤2中的检测采用在线拉曼光谱。
  12. 根据权利要求1～11任一项所述方法，其特征在于，所述步骤2中的胺酸摩尔比为1.005-1.05，优选为1.01-1.04。
  13. 根据权利要求1～12任一项所述方法，其特征在于，脱水的温度为170-260℃，压力为0.7-2.0MPa，脱水时间为10-40min；所述预聚反应的温度为250-350℃，压力为10-30MPa，反应时间为1-15min；所述后缩聚反应的反应温度为300-350℃，反应时间为0.5-5min。
  14. 根据权利要求1～13任一项所述方法，其特征在于，所述步骤2中脱水工序产生的水蒸汽可作为热源用于浆料的升温、溶解，多余水蒸汽可在冷凝后与升温工序中产生的冷凝水合并作为补加水用于形成浆料的工序。
  15. 一种半芳香族聚酰胺，其根据权利要求1～14任一项所述方法制备得到，其凝胶含量为1.0％以下，优选为0.8％以下。
  16. 一种半芳香族聚酰胺，其特征在于，其通过二元酸与脂肪族二元胺经缩聚反应而得到，所述二元酸包括芳香族二元酸、脂肪族二元酸，所述芳 香族二元酸与脂肪族二元酸的摩尔比为100：0～40：60，优选为100：0～50：50；其凝胶含量为1.0％以下，优选为0.8％以下；其特性粘度为0.7～1.0dL/g。
  17. 根据权利要求16所述的半芳香族聚酰胺，其特征在于，所述脂肪族二元酸选自丁二酸、戊二酸、己二酸、辛二酸、壬二酸、癸二酸、十二烷二酸中的一种或几种，所述芳香族二元酸选自间苯二甲酸、对苯二甲酸、萘二甲酸中的一种或几种；所述二元胺选自己二胺、庚二胺、辛二胺、壬二胺、癸二胺、2-甲基戊二胺、十一亚甲基二胺、十二亚甲基二胺、苯二亚甲基二胺中的一种或几种，优选所述二元胺选自己二胺、辛二胺、癸二胺中的一种或几种。
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